Low-boilina oil esom hicrhek-boilihg petroleum ob belated oil



names! is. com, or :rEnsEY crrnnaw JERSE Assrenon r0 STANDARD on.COMPANY,

or BAYONNE, nEw JERSEY, A conroan'rxon or NEW JERSEY.

ammo Low-Bourneon. mom HIGHER-BOILING PETROLEUM on RELATED on.

aeaaets.

l lo Drawing.

To all whom it may camera:

Be it known that I, ERNEs'r B. COBB, a citizen ofthe United States,residing at Jersey City, in the county of Hudson and State of NewJersey, have invented certain new and useful Improvements in MakingLow-Boilin Oil from Higher-Boiling Petroleum or elated Oil, of which thefollowing is a specification.

his invention relates to obtaining 011s which arecomposed mainly atleast of hydescription which are mainly at'least composed ofhydrocarbons with viscosities too low for normal constituents of otherthan li ht grades of lubricants (say with viscosities under one hundredand seventv seconds at 100 F. with an Engler viscosimeter with whichwater exhibits a viscosity of fiftythree seconds at 60 F.) such as theinferior grades of burning oil (kerosene) (either finished or untreated)and the oils commonly disposed of as gas oil or fuel oil on account oftheir being unfit on the one hand for burning oil (kerosene) and on theother for medium and heavy lubricants; for which products there isusually a good demand at higher prices than those of gas oil or fueloil.

In accordance with the invention, pe-

troleum in appropriate form is distilled with anhydrous aluminum chlorid(Al Cl in solution in (combination with) a part of the oil operated upon(useful proportions hereinafter indicated) at temperatures sufficient tosplit up component hydrocarbons of the oil; and the products of suchdistillation are fractionated to obtain oils of such grades as may bedesired and obtainable.

Said distillation with anhydrous aluminum chloridis continued to suchextent as may be desired. By continuing it until a Specification ofLetters Patent.

Patented Nov. 25, 1919,.

Application filed April 25, 1914. Serial No. 884,344.

dry or nearly dry residue remains in the still, practically the entirecarbon content of the oil operated upon, except the portion whichescapes as gas or as uncondensed vapors or is otherwise lost, isobtained'in the forms of distillate from distilling in the presence ofanhydrous aluminum chlorid and of coke respectively.

Should the distillation be terminated previously, that is to say, whilethe residual material is yet liquid as a whole or in substantialproportion, the carbon content of theoil operated upon can also beobtained 11 said forms respectively, by separating the oily portion ofthe residual material from the aluminum chlorid thereof and (if desired)also from the solid carbonaceous matter (1f any) which may be presenttherein, and subjecting the hydrocarbons of said oily portion todistillation with anhydrous alumlnum chlorid. The so separated oilyportion can be distilled at once with anhydrous aluminum chlorid, but itwould best be distilled by itself to dryness or nearly so, and theresulting distillate then be distilled with anhydrous aluminum chlorid.

The said oily portion can, however, be disposed of otherwise as may bepreferred; in case it should not be desired to distil its componenthydrocarbons with anhydrous aluminum chlorid.

In distilling with anhydrous aluminum chlorid the activity of the latterdiminishes with the progress .of the distillation; and of thetemperature of the oil in distillation should be kept approximatelyconstant, after a suitable flow of the distillate has been established,the delivery is liable to diminish down to an impracticably slow rate,andeventually to cease altogether; and this diminution (or cessation) ofdistillation, in distilling at constant temperature,

occurs sooner the less the proportion of an-- more than ten per cent. byweight of the original charge of oil operated on (less than I tenpercent. in fact) will exert its activity continued to dryness orapproximately so.

The aluminum chlorid is easily separated temperature, and allowing theresulting:

substantiallyto the end of a run, which-is in its entirety from itsoriginal solution in a part of'the oil operated upon, by washing suchsolution with water at say atmospheric num'in a sample after the latterhas been I boiled say for ten minutes in water.

By further distillation at increasing temperature, less and less of thealuminum chlorid is found to be separable in this manner; so thateventually the major portion of the aluminum chlorid will be retained.The union with carbonaceous matter may in fact become so strong thatlittle 4 (if any) of the aluminum chlorid can be extracted from theresidual material by boiling water as aforesaid.

In case, therefore, the aluminum chlorid is to be recovered by washingout, it is desirable not to proceed too far with the distillation; but,in view of the fact that the farther the distillation is carried, thegreater the conversion effected by a given amount of aluminum chlorid,it is desirable on this account to proceed at least until the residualmaterial attains approximately the lowest point at which practically allof the aluminum chlorid can be washed out with water.

Any ordinary or suitable distilling apparatus can be used. An ordinarystill of horizontal cylindrical form holding say six hundred barrels offorty gallons each and an ordinary watercooled condenser connected withsaid still by a vapor pipe will answer. The following examples are givenby way of illustration and not as restricting the invention to them orto details of them.

Such a still may well receive a charge of about four hundred barrels ofthe gas oil or fuel oil mentioned, and a limited proportion;

not more than about ten per cent. by weight of anhydrous aluminumchlorid. The temperature isgradually raised until distillate commencesto flow from the condenser outlet (which may be 'in say six or eighthours or there about from the commencement of firing); and the fires areregulated to give barrels an,

tion increases gradually, as is required in order to distil at anindustrially; practicable rate. The run is terminated sooner or later,according to It may, for example, be carried on until the contents ofthe still constitute an at least approximately dry residue; or it may beterminated while the residual material is liquid in whole or inasubstantial proportion. It may be terminated while the stlll contentsare of a character to permit the practicable separation ofaluminumchlorid from the remaining material by washing out; or it can be carriedso far that the'separation, 1f any, which can thus be effected is notenough to be practicable.

Atthe close of the run, the heating is discontinued, and later, when therunning (if any) from the condenser outlet has ceased, the residualmaterial is removed from the still preparatory to charging the still fora a new run; If said residual material is sufliand the aluminum chloridtherein (or its elements) can-be recovered and disposed of, in anyappropriate way. The oily or other carbonaceous matter in said resldualmaterial can also be recovered and disposed of I as preferred. Forexample, by combustion of the residual material (in whatever condition)an ash consisting almost wholly of alumina is obtained, and also gasescontaining hydrochloric acid. If the residual material is of a characterto allow a practicable separation of aluminum chlorid by washing out, itis advantageously washed with water of appropriate temperature, say ator above 150 F., using as little water as will suflice, say about twentyfive per cent. of the residue, or possibly a smaller amount; especiallyif the washing is conducted in a systematic manner by transferring thewash water from a previously washed residue to residue whichhas not beenwashed to the same extent, if at all. An aqueous solution of hydratedaluminum chlorid is thus obtained, which can be disposed of in anyappropriate way. By evaporation of it' to dryness, alumina is obtainedas residue and hydrchloric, acid passes OK with the water vapor. If theresidual material is liquid in whole or in substantial proportion,washing aqueous solution of hydrated aluminum chlorid. The so recoveredoil is advanaluminum chlorid. The coke from distillin the recovered oilto dryness can be dispos of as may be preferred. The recovered oil I canbe distilled at once with anhydrous aluminum chlorid, although not soadvanmasses means from hydrochloric. acid) is passed over anincandescent mixture of coke and alumina.

Returning to the distillation of the petro-' leum (gas oil as mentioned)with anhydrous aluminum chlorid, it suflices to collect the distillateall in one receiver. Any solution of anhydrous aluminum chlorid whichmay come over with distillate is allowed to settle out and is separatedfor. future 'use. The condenser and a liquid separator intermediate thecondenser and the distillate receiver may well be elevated above thestill, and the bottom of the separator be connected with the still by asuitably trapped pipe for conducting the aluminum chlorid solution backto the oil in distillation; while the upper part of the separator isconnected with the distillate receiver.

The distillate may be washed with water and then fractionated withpartial or with complete distillation by means of dry heat; or thefractionation may be performed by partial distillation in a steam still,in whic case the water of condensation serves to wash the distillate.Washing the distillate with water can precede the steam stilling, ifpreferred; and the residual oil from partial distillation with dry heator in the steam still can be fractionated by dry. heat, or can bedisposed of otherwise, as may be preferred. Iii-some cases at least itmay be best to agitate the washed distillate with sufficient alkali(caustic soda lye) to neutralize any remaining acid (hydrochloric acid)therein before fractionating by distillation. In fractionation, cuts aremade to obtain oils of the desired grades, all of which may well becomposed at least mainly of hydrocarbons with boiling oints notexceeding 450 F. and also to o tain, if desired, higher boiling oils.The low boiling oils, say various grades of naphtha, may be finished foruse or sale by giving them the customary treatment with sulfuric acidand alkali; and the burning oil (kerosene) distillate can be similarlyfinished. The higher boiling oils, as a whole or in such part as may bepreferred, can be distilled anew with aluminum chlorid; or ,they can bedisposed of otherwise, as may be preferred.

Good results have been obtained in a small way with an amount ofanhydrous aluminum chlorid equal to about seven per cent. by weight ofthe oil operated upon; nine per results. The proportlon can cent. byWeight would probably give betteg e varle within wide limits. Reductionof the proportion of anhydrous aluminum chloridtends to lower the yield.of hydrocarbons with boiling points below 450 F. Increase in theproportion of anhydrous aluminum chlorid tends to increase theproportion of such hydrocarbons; but it Will probably not be worth whileto exceed about ten per cent. by weight in any case. If this percentagebe aluminum chlorid dissolves at appropriately elevated temperature in apart of such d s-- agitation, The anhydrous aluminum ch10 ridcan beadded to the oilin thestill in solid state or in solution; or it canbeplaced added to petroleum distillate (gas oil or fuel ,oil or, other.distillate) the; anhydrous in the still before charging the same withi' oil. When the still is heated the aluminum chlorid dissolvesgradually in a part of the oil when the temperature sufiices. Probablyif enough aluminum chlorid were employs the whole of the oil might forma solution thereof; but it is'not be ieved that so large a proportionwould be desirable, practicable.

From gas oil or fuel oil containing some parafiin wax and of a gravityof 33.8 B.,

which consisted of over ninety per cent. by

volume of hydrocarbons with boilin points above 450 F. and which, ifdistilled in the usual Way in a laboratory flask, would give firstrunnings equal to five per cent. by

volume with a gravity of 48 3, an amount of naphtha (distilling ove'r upto 302 F.) of 67 B. equal to about twenty anda half per cent. by volumeof said gas oil or fuel oil and water white burning oil (kerosene) of45:6" B. equal to twenty nine per cent. by volume of said gas oil orfuel oil have been obtained, using about 7% by weight of anhydrousaluminum chlorid and working in a small way. These oils consisted thenaphtha wholly and the kerosene mainly of hydrocarbons with boilingpoints not exceeding 450 F. The first 5% runnings of the distillate hada gravity of 80.7 B. The naphtha hydrocarbons have been found to bemainly at least of a saturated character, exhibiting small heatingeffect, as compared with naphtha produced in the ordinary crackingofcrude petroleum, when shaken up 20 7 low grade and about 45.3" B.gravity" obfree from paraffin wax and having a gravity of 403 B., whichconsisted over thirty per cent. of hydrocarbons with boiling oints above450 F. and which, if distilled 1n the usual way in a laboratory flask,would give first runnings equal to five per cent. by volume having agravity of 51.9 B. there has 'been obtained (using about 7% by weight ofanhydrous aluminum chlorid and work- 'ingin a small way) a yield ofnearly twenty seven percent. by volume of naphtha of 57.7 B. gravity,composed wholly of hydro carbons with boiling pointsup to 302 F. (firstrunnings equal to five per cent. by volume of the oiloperated uponhaving a gravity of;71 B.) and about sixty per cent. of burning oil(kerosene), distillate over ninety five per cent. of whose hydrocarbonshad boiling points not exceedin 4 50. F.

From finished burning oil erosene) of tained mostly from Pennsylvaniaand Limacrude petroleum (in part from each), using about 7% by Weight ofaluminumc-hlorid and working in a small way, about 24.5% by volume ofnaphtha of 687 B. distillin over up to 302 F. (first 5% runningsof 603B.

' The temperatures of the oil in distillation and other things will varyconsider ably, according to the character of. the starting material andother circumstances. In

a small scale test run (which was made sub-' sequentlyto the filing ofthe application for the present patent by way of example in order toillustrate a particular case in detail 16 and in which a charge of2,500'cubic' centi- -meters of a gas oil of 344 B. gravity was distilledwith anhydrous aluminum chlorid to dryness) the oilinflistillationshowed a temperature of 315 F. when distillate commencedto flow from the condenser outlet (about an hour and twenty five minutesafter commencement of firing)" and a temperature of nearly 700 F. whenless than one per cent. of obtainable distillate remained in the still(about eleven hours and forty five minutes later). vThe observedtemperature of the vapors passing over to be condensed as distillate.was 200 F. when distillate commenced to flow from the condenser outletand 470 F. when the oil had been distilled to. the. above mentionedstate of approximate dryness. lnthis testrun one hundred and fifty gramsof anhydrous aluminum chlorid (equal to seven per cent.

the start.

the vapors which were condensed as distillate. The first of thefollowing tables by Weight of the original still charge) were 1 Iemployed, the whole being introduced at" The distillate was collected insixteen fractions, each equal to five per cent.

(Table 'A) shows the gravities of the sev- I eral fractions, therespective temperatures of the oil in distillation and the vaporspassing over to be condensed as distillate at the,

close of each collection, and the time oc-jfcupied in each collection.The second table I (Table B) gives the results of assays of the j 1several 5% fractions of distillate and shows 1.. j.

the percentages of each fraction with boiling points up to 302 F., 350F.,1450 F. and 572 F.,'respectively. This table also shows (1) the finaltemperatureof the]; pors in the flask neck in each assay in which suchfinal temperature was below 572 -'F.Q, (2) the percentage ofoilremaininginthe flask at the close of the assay in each case y I in whichthevapors in the flask neck. at-" tained a temperature of 572 F., and (3)the percentage of loss 1n each assay.

Table A.

. Fractiors (laistillalatejper gfi gfg tolill 1 225;; Time,

. 11 m 5 s i 0e y v0 u e B over .F minutes 00.1 402 31s 40 63.8 434 32035 59.2 472 340 4 30 57.5 502 35s 35 56.1 534 376 40 55.0 557 505' 5054.5 500 390 40 54.2 570 420 35. 53.8 572 420 40 55. l 581 424 40 55.5500 434 45 55.5 500 440 50 54.1 515 450 55 54.2 035 475 55 53.0 050 47550 55.9 002 470 05 54.8 000+ 480 55 Table B.

Fractions distillate, Sper 302 350 450 572 Final, Bot- L cent. by vol-F. F. F. F. T. toms.

ume.

Perot. Perct. Perot. Perot. Perot. Perot. Perot. 75.0 83.0 89.0 91.0 4900. 70.0 20.0 86.5 02.0 543 s. 57.0 71.0 85.0 93.0 550 7. 49.0 63.5 82.093.5 560 6. 43; O 57. 0 78. 0 94. 0 560 6. 42.0 55.0 75.5 00.5 558 0.36. 0 4S. 0 74. O 95. 0 565 5. 35.0 47.0 07.5 94. 5. 570 5. 33. 0 43. 564. 0 94. O 2. 0 4. 35.0 45.0 53.0 05.0 558 5. 39. 0 49.0 68. 0 93. 0 3.0 4. 36. 0 46.0 66.0 95. 0 570 5. 32.0 41.0 57.0 91.0 7.0 2. 31. 0 40. 055. 0 89. O 9. 0 2. 30.0 38.5 50.0 73.0 25.0 2. 35.0 45.0 58.0 74.5 23.52.

An assay of a specimen of the gas 011 haaaere charged (344 B. gravity)showed the following percentages:

may be made of petroleum in undistilled forms, reduction (partialdistillation) of crude petroleum with or without injection ofsuperheated steam into the oil; but it is considered less advantageousto operate upon un distilled petroleum than upon distillates on accountof the larger proportion of carbon in the former.

' Gas oil yields more carbon oil (kerosene). A considerable amount ofgas and light vapors, which would escape condensation in the ordinarywater cooled condenser, would also be formed in any case.

Distillates of higher boiling hydrocarbons than those of the gas oil orfuel oil mentioned (such as heavy paraffin distillate or pressedparaflin distillate, or even residue from partially distilling presseddistillate). can be operated upon; but it is considered that to do sowould be less advantageous than to operate on gas oil or fuel oil, orlow grade burning oil (kerosene) (finished oil or untreated distillate).The distillates obtained in reducing pressed paraffin distillate can beoperated upon; and, in fact, the lighter portion of such distillate(when available) commonly forms part of the gas oil or fuel oilmentioned. So-called acid oil, obtained in known ways from acid sludgefrom treating burning oil (kerosene) distillate and lubricant stock (oneor other, or both) with sulfuric acid (usually acid of 66 13., sometimesstronger) can be operated upon, alone or in mixtures. Hydrocarbon oilswhich are not forms of petroleum, but have a suitably close relationthereto, such as shale oils and the like, canbe operated upon.

The fractionation of the distillate from the distillation with anhydrousaluminum chlorid, instead of being performed wholly in a distinctdistillation, may be performed at least in part in the distillation withanhydrous aluminum chlorid by means of a partial condensation or aseries of partial condensations of the vapors. Condensate or one or morecondensates from such partial condensation or condensations can be re-.

turned to the oil in distillation or can be col lected as distillate, asmay be preferred. -The partial condensers (one or more) may be aircooled or liquid cooled. They may receive the vapors at or near thebottom, so

as crude petroleum, or residues from than burning oil (kerosene) orother that these pass in tact with retrograding condensate; or they mayreceive the vapors at or near the top, so that the, vapors, as well asthe condensate, travel downward.

The distillation with anhydrous aluminum chloridis not necessarilyperformed by charging a still and then running off the charge. lesscontinuous manner. Oil might be supplied to the charge in the stillwhile the distillation is going on, with or without addition thereto ofanhydrous aluminum chlorid,

It maybe performed in a more oropposite directions in conand with orwithout the withdrawal of residual oil during the run. Continuous stillsof any known or suitable form can be used.

Distillate from the distillation with anhydrous aluminum chlorid can betreated with sulfuric acid and alkali prior to fractionation by furtherdistillation; but it is considered better to apply such treatment tofully fractionated oils.

Other materials not inconsistent with the action of the aliiminumchlorid on hydrocarbons can, ofcourse, be used in addition thereto.Anhydrous perchlorid of iron (Fe Ol if used inaddition to the anhydrousaluminum chlorid, is believed to comchlorid of iron and aluminum; whichacts similarly to the aluminum chlorid; a difference in reaction hasbeen observed; and probably a number of other substances would actsimilarly. In naming aluminum chlorid, therefore, in the hereinafterwritten claims, it will be understood that double chlorid of iron. andaluminum and other similarly actingsubstances are intended to beincluded and'not excluded by such recital.

In stating in the hereinafter written claims that the petroleum orrelated oil is to be in' any appropriate form, it is to be understoodthat gas oil or fuel oil, burning like form is primarily but notnecessarily exclusively intended. In consequence of oflicial requirementof division, an application (oflicially numbered 186,542), for part ofthe subject-matter set forth hereinabove, was filed August 16, 1917, asa division andcontinuation of the application for the present patent.

On. July 14 and October 4, 1919, applications (officially numbered310,875 and. 328,578, respectively) were also filed for part of thesubject-matter herein above set forth. Each of them is a continuation ofthe application for the present patent; and each of them, moreover, hasbeen made under section 4897, Revised Statutes, for the invention ordiscovery of my said divisional appication No. 186,542, allowed October6, 191

I claim as my invention or discovery: 1. The process of making lowboiling oil although bine with thelatter and so to form a double fromhigher boiling petroleum or related oil,

consisting in distilling petroleum or related oil in any appropriateform with anhydrous aluminum chlorid in solution in a part of the oiloperated upon, and conducting operations in such manner that practicallythe entire carbon content of the oil operated. upon, except theportionwhich escapes as gas or as uncondensedvapors or is otherwiselost, is obtained the main part thereof in the form. of distillate fromdistillation in the presence of said anhydrous aluminum chlorid and theremaining smaller part of said carbon content in the form of coke,substantially as described;

2. The process of makinglow boiling oil from higher boiling petroleum orrelated oil, consisting in distilling petroleum or related oil in anyappropriate form with anhydrous aluminum chlorid in solution in a partof the oil operated upon at least until the residue approximates thelowest point at which it can be freed from aluminum by boiling withwater, substantially as described. I

3. The process of making low boiling oil from higher boiling petroleumor related oil, consisting in distilling petroleum or related oil in anyappropriate form with a limited proportion, not more than about ten percent. by weight, of anhydrous aluminum chlorid in solution in a part ofthe oil operated upon, conducting the distillation with such regulationof the fires as to maintain a good flow of distillat from the condenseroutlet by reason of the rising temperature of the oil operated upon, andcontinuing the distillation with rising temperature in said oil at leastuntil the residue approximates the lowest point at which it can be freedfrom aluminum by boiling with water, substantially as described.

4. The process of making low bolling oil from higher boiling petroleumor related oil,

consisting in distilling petroleum or related oil in any appropriateform with anhydrous aluminum chlorid in solution in a part of the oiloperated upon until the residue is reduced to an at least approximatelydry condition, substantially as described.

5. The process of making low-boiling oil cent. by weight, of anhydrousaluminum chlorid in solution in a part of the oil operated upon,conducting the distillation with such regulation of the fires as tomaintain a good flow of distillate from the condenser outlet by reasonof the rising temperature of the oil operated upon, and continuing thedistillation with rising temperature in said oil until the residue isreduced to an at least approximately dry condition, substantially asdescribed.

6. The process of making low-boiling oil from higher boiling petroleumor related oil, consisting in distillingpetroleum or related oil in anyappropriate form with anhydrous aluminum chlorid in solution in a partof the oil operated upon, conducting the distillation with suchregulation of the fires, as

to maintain a good fiow of distillate from the condenser outlet byreason of the rising temperature of theoil operated upon, and continuingthe distillation with rising temperature insaid oil until at leastapproxi mately the end of the run, substantially as described.

7. The process of making low-boiling oil from higher boiling petroleumor related oil, consisting in distilling petroleum or related oil in anyappropriate form with a limited proportion, not more than about ten percent. by weight, of anhydrous aluminum chlorid in solution in a part ofthe oil operated upon, conducting the distillation with such regulationof the fires as to maintain a good flow of distillate from the condenseroutlet by reason of the rising temperature of the oil operated upon, andcontinuing the distillation with rising temperature in said ERNEST B.COBB.

l/Vitnesses:

C. M. FORREST, CORA H. TRACY.

